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By M. Muskat

A theory has been developed describing the behavior of wells and reservoirs producing by the action of bottom water drives. It is assumed that the pressures are maintained above the bubble point, and that the permeability to viscosity ratio of the water in the flooded zone is the same as for the oil in the oil-saturated pay. Accordingly, the treatment is based on the homogeneous fluid potential theory. The effect of the difference in density between the oil and water is neglected. .4fter deriving the proper potential distrihutions, the nature of the rise of the water-oil interface below the producing wells is calculated. The primary clean-oil-production phase is expressed in terms of the displacement efficiency, defined as the fraction of the pay flooded out by the rising water table at tlle time of first water entry. The variation of this displacement efficiency is calculated as a function of the well spacing, pay thickness, the ratio of the horizontal to vertical permeability, and the well penetration. The important parameter, other than the well penetration, is found to be the ratio of the well separation to the thickness of the oil pay multiplied by the square root of the ratio of vertical to horizontal permeability. It was found that the displacement efficiency continually decreases as this parameter increases, and for values of the latter >3.5, the efficiency varies inversely as the square of the parameter. It also increases with decreasing well penetration. Perhaps the most striking result of this phase of the analysis is the conclusion that in order to explain the delay in entry of water in wells producing by bottom water drives for periods longer than a few days normal production, with drawdowns large compared with the differential density head between the oil and water, it is necessary to assume that the vertical permeability is a very low fraction of the horizontal permeability. An analysis is also given of the production history after the water has broken through, on the assumption that the production mechanism and details of the flow distribution continue to be the same as during the phase of clean-oil production. As is to be expected, it is found that the water cut will increase at an accelerated rate as production proceeds. However, the initial differences between systems of different well penetrations or well spacings with respect to the total clean-oil production gradually decrease in terms of the variation of the water-oil ratio with cumulative production. In particular, by the time the water-oil ratio has reached values of the order of 5 or greater the cumulative recoveries will generally differ much less among various producing systems than their corresponding clean-oil recoveries. Introduction On the basis of elementary geological principles, one may classify effective water-drive fields in two groups. In the first, the entry of water into the oil-producing formation may be characterized as an edge-water encroachment. This term is used to suggest that the motion of the water proceeds largely in a direction parallel to the planes of stratification. This type of water intrusion occurs usually in thin producing zones and in strata lying along structural flanks of appreciable dip. In the second group—"bottom water-drive" fields—the water-oil interface lies in a plane of zero or slight inclination to the

Jan 1, 1947

By M. Muskat

A theory has been developed describing the behavior of wells and reservoirs producing by the action of bottom water drives. It is assumed that the pressures are maintained above the bubble point, and that the permeability to viscosity ratio of the water in the flooded zone is the same as for the oil in the oil-saturated pay. Accordingly, the treatment is based on the homogeneous fluid potential theory. The effect of the difference in density between the oil and water is neglected. .4fter deriving the proper potential distrihutions, the nature of the rise of the water-oil interface below the producing wells is calculated. The primary clean-oil-production phase is expressed in terms of the displacement efficiency, defined as the fraction of the pay flooded out by the rising water table at tlle time of first water entry. The variation of this displacement efficiency is calculated as a function of the well spacing, pay thickness, the ratio of the horizontal to vertical permeability, and the well penetration. The important parameter, other than the well penetration, is found to be the ratio of the well separation to the thickness of the oil pay multiplied by the square root of the ratio of vertical to horizontal permeability. It was found that the displacement efficiency continually decreases as this parameter increases, and for values of the latter >3.5, the efficiency varies inversely as the square of the parameter. It also increases with decreasing well penetration. Perhaps the most striking result of this phase of the analysis is the conclusion that in order to explain the delay in entry of water in wells producing by bottom water drives for periods longer than a few days normal production, with drawdowns large compared with the differential density head between the oil and water, it is necessary to assume that the vertical permeability is a very low fraction of the horizontal permeability. An analysis is also given of the production history after the water has broken through, on the assumption that the production mechanism and details of the flow distribution continue to be the same as during the phase of clean-oil production. As is to be expected, it is found that the water cut will increase at an accelerated rate as production proceeds. However, the initial differences between systems of different well penetrations or well spacings with respect to the total clean-oil production gradually decrease in terms of the variation of the water-oil ratio with cumulative production. In particular, by the time the water-oil ratio has reached values of the order of 5 or greater the cumulative recoveries will generally differ much less among various producing systems than their corresponding clean-oil recoveries. Introduction On the basis of elementary geological principles, one may classify effective water-drive fields in two groups. In the first, the entry of water into the oil-producing formation may be characterized as an edge-water encroachment. This term is used to suggest that the motion of the water proceeds largely in a direction parallel to the planes of stratification. This type of water intrusion occurs usually in thin producing zones and in strata lying along structural flanks of appreciable dip. In the second group—"bottom water-drive" fields—the water-oil interface lies in a plane of zero or slight inclination to the

Jan 1, 1947

By Harold S. Morgan

INTRODUCTION The Waste Isolation Pilot Plant (WIPP) is being developed in southeastern New Mexico by the United States Department of Energy as a research and development (R&D) facility to demonstrate the safe disposal in salt of radioactive wastes resulting from defense activities. As part of the WIPP R&D program, a series of in situ tests will be performed to determine the behavior of drifts and storage rooms in the creeping salt medium (Matalucci, et al. 1982). Data obtained in these tests will be used to evaluate and improve numerical models used to compute the structural response of these drifts and rooms. Stress has been proposed as one of the parameters to be measured in the tests, and borehole inclusion stressmeters have been included in the instrumentation package. Cages of this type provide an indirect measurement of stress change in that they actually monitor borehole displacements which are then related to changes in the in situ stress away from the borehole. The relationship between stress and displacement is highly dependent upon the constitutive behavior of the rock in which the gage is emplaced. This relationship is well understood for rocks with linear stress-strain behavior (Fossum, et al, 1976), but, for creeping rocks like salt, the relationship has yet to be determined. Thus, inclusion gage response in salt must be investigated fully before stress measurements from the WIPP in situ tests can be used for comparisons with computed stresses The calculations presented in this paper were performed as part of an investigation of inclusion stressmeter performance in salt. They focus on the strain gaged stressmeter (SGS) (Cook and Ames, 1979) and on a hypothetical solid cylindrical inclusion with variable stiffness Issues addressed include the effects of creep and the effects of gage stiffness on stressmeter output for various loading conditions. The

Jan 1, 1984

By T. A. Wright

THE SAMPLING of waste materials containing copper, lead and tin has taken on a new significance within recent years, and is of increasing importance, on account of the entry of some of the copper refineries into this field and the tendency towards consolidations among the smelters. In the past, such material was sold on the basis either of a rough or grab sample or of casual inspection of the lot. The two principal sources of this waste are the processes of fabrication and the scrapping of automobile, electrical, plumbing, railroad and other equipment. In both cases much material can be sorted, salvaged and sold by classification and grade to be melted "as is" or with the addition of new or virgin metal. The increasing care in classifying exercised in the large manufacturing plants tends to increase the proportion of this usable scrap; on the contrary, the increasing use of more complex and special non-ferrous alloys tends to make sorting and grading more difficult in turnings, borings, clippings, etc., and consequently is making sampling of more moment. In tin, lead, aluminum, and zinc furnace by-products such as ashes, drosses, skimmings, etc., the trade practice of evaluation has not varied much. For instance, tin drosses, battery lead, and aluminum skimmings are ordinarily sold on what is called "metallic button" or "metallic recovery" or "metallic yield." Copper and lead waste, however, is being sold more and more on actual copper and lead contents based on sample and chemical analyses. This paper will be devoted chiefly to the sampling of materials suitable only for refining and recovery of one or more of the metals present. The methods described are often based on the fact that but one metal, such as copper, is to be paid for. The loss of volatile constituents in melting does not appreciably affect the final copper result, as the "after-melting" assay can he readily calculated to the "before-melting" basis, but if smelter efficiency continues to increase, so that in time zinc, for instance, may be recovered on a paying basis, the method of sampling dirty brass, for example, will have to be changed also. As a matter of fact, we may expect that improved refining processes will make possible the partial recovery of lead and tin which are now lost.

Jan 1, 1928

By James T. Gow, Oscar E. Harder, Anton de S. Brasunas

THIS paper deals with the results obtained and the techniques employed in determining: I. Liquidus and solidus temperatures of the HH and HT type heat-resistant alloys. † 2. The relation of true temperatures (thermocouple) to apparent temperatures (optical pyrometer) for the molten HH and HT type alloys. This work was the outgrowth of needing to know something definite about these temperatures in order to study the effect of pouring temperatures, shake-out times, and heat-treatments on the properties of some heat-resistant alloys. The information developed is thought to be of interest to industry for guidance in foundry practices and the industrial heat applications of the alloys. This paper is based upon work that has been done for the Alloy Casting Institute at Battelle Memorial Institute. LIQUIDUS AND SOLIDUS TEMPERATURES OF HH AND HT TYPE ALLOYS Experimental Procedures Temperature-time curves were obtained during the cooling and solidification of several HH and HT type alloys. The metal was melted in an Ajax high-frequency induction furnace and poured into a coresand mold for cooling. The temperature measurements were obtained by means of a platinum, platinumrhodium thermocouple contained within a fused silica sheath, which was extended through the side wall of the dry core-sand mold to a point at about the center of the mold cavity, which was 3 in. in diameter by 5 in. deep. The cold junction of the thermocouple was kept in an ice bottle, and the temperature was recorded automatically on a direct-reading potentiometer recorder. Through a switching arrangement, the temperature recorded was checked occasionally with a portable Leeds and Northrup potentiometer indicator. Less than a 5°F. variation in the two instruments was always found. This is within the limit of accuracy of readings. The thermocouple used was checked for accuracy against a standard couple, both before use on this work and after completion of the work, by the instrument laboratory. Temperature-time Cooling Curves Fig. I is an enlarged reproduction of a part of one of the cooling curves over the temperature range of 2600° to 2200°F. for an alloy of the HT type with 0.45 per cent carbon, 16 per cent chromium, and 36 per cent nickel. This is a typically shaped cooling curve as obtained for the alloys. It will be noted that two temperatures are shown on Fig. r for the liquidus temperature. It is thought likely that the higher temperature, A, at the point at

Jan 1, 1945

By L. B. McConville

The general term "tar sand" refers to sand that contains varying amounts of dense, viscous petroleum. Tar sand deposits have been found throughout the world, often in the same geographical area as conventional petroleum. The largest one by far is known as the Athabasca Tar Sands, in the province of Alberta, Canada. Actually a group of three deposits, these particular sands underlie an aggregate area of more than 12,000 sq miles. Current estimates place the contained raw petroleum at about 700 billion bbl; and via currently available technology, the amount of recoverable synthetic oil may be as much as 300 billion bbl-which is roughly equivalent to five times the combined US and Canadian total crude oil reserves. With the ever-widening gap between energy supply and demand, mining and petroleum companies are now evaluating all possible energy resources-both developed and underdeveloped-and, certainly, the Athabasca Tar Sand deposit is one of the more important ones to merit such attention. The first section in ME deals with the geology and historical developments; the other four sections, with mining methods, extraction technology, economics, and outlook.

Jan 1, 1975

By Ray Light, Everett M. White

Numerous articles have been written about the coal miner ; he has been compared with brave men who have gone out to conquer some unknown hazard throughout the ages. Now, however, modern mining is no longer something to be avoided, but a vocation that anyone can be proud of, with remuneration equal to or above that of almost any industry. A concerted effort is being made each day by both the operators of most mines as well as the state and federal inspectors to see that coal mines are as safe or safer than work places in any other industry. However, it is true that mine fires and explosions have occurred in the mining industry since its inception. One of the earliest accurate references to such an occurrence is found in the transactions of the Royal Society of London. In the Colliery Managers' Handbook, 1898, Caleb Pamely writes of an explosion that occurred at Fatfield, England in August 1708, resulting in the deaths of 69 persons. He states: "Three of them, viz, two men and a woman, were blown quite up from the bottom of the shaft, fifty-seven fathoms deep, into the air, to a considerable distance from the mouth of the pit." It is interesting to note that women were employed as miners in England during that period. In the United States, the first record of coal mined was in 1702 by the Jamestown colonists. In 1786, about 20 years after Pittsburgh, PA was first settled, a charter was granted by William Penn to mine coal on the banks of the Monongahela River. Then in 1803, the first important coal company, the Lehigh Coal Co., was established. From this beginning, the mining industry continued to grow in importance and the first state mining law was formulated in 1870. The Pennsylvania state mining law was followed in 1873 by Ohio's, and in 1876 by Maryland's. A mine explosion at Avondale, PA in 1869 stimulated state legislatures to formulate these early laws. In 1907 near the town of Fairmont, WV, there were, within three days, two explosions resulting in a total of 597

Jan 1, 1981

By Robert Mehl

THE importance of the Widmanstätten structure to structure theory in metallography has been recognized by many writers.1 It is a structure produced by the precipitation of a new phase from a solid solution upon cooling as a result of changing solid solubility, and displays a characteristic appearance indicating a crystallographic relationship between the new phase and the original solid solution (Fig. 1). First discovered in 1808 by Alois de Widmanstätten2, the structure has been traced by analogy through many alloy systems. Particularly is this true of the steels. Sorby's classic work3 on the microstructure of iron and steel was in essence an attempt to explain the origin of this characteristic structure in meteoric iron. He observed in a Bessemer steel and in a cast-steel ingot structures which we now recognize as typical Widmanstätten figures.4 Osmond5 observed structures in a steel ingot analogous to those found in meteorites. Arnold and McWilliams6 obtained (and recognized) a

Jan 1, 1930

By Fred Bond

This paper is a continuation of two earlier papers,1,2 and presents new data on the grindability of various ores and other materials-the results of several years of intermittent research work on the nature of grinding and interpretation of test results. It is divided into five parts: 1. The tabulated results of several hundred grindability tests on a wide variety of ores. 2. A method of correcting screen analyses and calculating from them the surface and other properties. 3. A description of a. new method of measuring the "surface energy" of in ore by pendulum impact tests. 4. Test results. 5. A general discussion of the test results and their application to grinding problems.

Jan 1, 1938

By P. Chiotti, R. J. Hecht

Vapov pressure data of solid and liquid alloys along with phase diagram data WERE employed in calculating the thermodynamic properties for the Ca-Zn system. The relative excess partial molal free energy for zinc in the liquid alloys was fitted to the relation wnvre i is we tvmpvrutiirc in ucgrees neivtu ana in is the tr~ole fvaction. Relations for the standard free energy of fortnation for the eight cornpounds were developed. ThE phase diagram for the Ca-Zn system as determined by Messing et a1.' is reproduced in Fig. 1. Earlier work on the phase diagram has been summarized by Hansen and Anderko2 and the very limited thermodynamic information for this system has been reviewed by Hultgren et a1.3 The heat of fusion for the compound CaZn2 has recently been determined to be 9260 cal per mole.4 Solubility data for calcium in zinc for the temperature range of 650" to 725°C were fitted by the relation and reported by Johnson and Dilloon5 In the present investigation zinc vapor pressure data were obtained by both the dewpoint and Knudsen methods in order to calculate the thermodynamic properties for liquid and solid alloys. The dewpoint method as employed in this work requires that only one of the components be significantly volatile, in this case zinc, and that the vapor pressure of pure zinc be known. For calculation purposes the vapor pressure data for pure zinc3 were fitted to the relations; for temperatures below 692.7K, the melting point of zinc. The corresponding free-energy relations for vaporization and sublimation of pure zinc are respectively. Some of the calculations also required knowledge of the free energy of fusion of zinc and calcium and the free energy for the 721°K allotropic transformation of calcium. The free energy of fusion of zinc was taken to be the difference between Eqs. [4] and [5], or The free energy of fusion and transition for calcium were based on the enthalpy values of 2040 and 222 cal per g-atom, respectively, as reported by Chiotti et al. 4 and the heat capacity data given by Hultgren et a1.3 and are represented by the relations, In the latter expression the difference in heat capacity between the a and 0 forms of calcium was neglected. MATERIALS AND EXPERIMENTAL PROCEDURES The metals used in preparing the alloys were Bunker Hill slab zinc, 99.99 pct pure, and Ames Laboratory calcium. The average impurities in the calcium in parts per million by weight, ppm, were N-17, H—77, Ba—216, Mg-15, Si—7, C—157, and Fe—9. The zinc was cleaned in dilute nitric acid and the calcium was used as received. The calcium was stored and handled in an argon-filled glove box and when removed from the dry box it was kept in an argon-filled desiccator. Tantalum was found to be a suitable alloy container. The alloy components were contained in a 1-in.-diam cylindri-

Jan 1, 1968

By C. M. Sellars, F. Maak

Electvomotie -force measurements hazle been made on ten Au-Ni alloys at temperatures 7754 825O, 900O, and 935°C using galvanic cells with solid electrolyte. Partial and ivtegral thermodynamic functions are derived from the determined activities. which show la9,ge positive deviations jvom Raoult's law. The enthalpies of mixing- are in close accord with calorinletric data and are of comparable accuracy. The results are used to determine the miscibility gap and the spinoidal curL1e, and are qlalitaticely interpreted in terms of the large size difference and electvonic interactions between gold and nickel. Tabulated nalues of the actielities and partial and inteqal free energies, entropies , and enthalpies of mixing are given in the appendix. The Au-Ni binary alloys are of particular interest thermodynamically as despite the large size difference between gold and nickel atoms they have a simple phase diagram.' This shows complete solid solubility above a miscibility gap with a maximum at about 71 at. pct Ni and 810°C. Activity measurements (over a range of temperature) have been made previously on this system using an electrolytic-cell method with a liquid chloride eletrolyte. The accuracy of this data has, however, been queried3'4 as it leads to values for the enthalpy of mixing which are too high when compared with calorimetric measurements.46 Also, the entropy of mixing is too high when compared with the values derived from specific-heat measrements. It was therefore considered worthwhile redetermining the activity data using a galvanic cell with a solid electrolyte (0.85 ZrO, 0.15 CaO). This method is based on a technique introduced by Kiukkola and aner'' and has been used to determine the thermodynamic data for Cu-Ni alloys.' THE ELECTROLYTIC CELL The cell used to determine the activity of nickel in Au-Ni alloys was: The cell reaction, which is discussed for a similar cell by Rapp and Maak, gives a direct measurement of the activity of nickel in the alloys as where aNi(alloy) is the activity of nickel in the alloy, 3 is Faraday's constant, E is the measured electromotive force, R is the gas constant, and T is absolute temperature. For the valid application of this type of cell the arrangement must be ther modynamic ally stable, which means that: 1) The free energies of formation of the oxides fulfill the relation 2) The vapor pressures or dissociation pressures of each component must be so small that during the time of the experiment the amount of any material transported by the gas is negligible. 3) Side reactions which change the alloy composition must be negligible. These reactions are possible both with the surrounding gas atmosphere and with neighboring solid material. The first two conditions are fulfilled by the above cell.' The third condition is approached by care in the experimental technique. The factors which control the attainment of equilibrium in this type of cell have been considered by Rapp and aak, who conclude that metallic diffusion in the alloy is the rate-control ling step. A lower temperature limit for the practical application of this cell is therefore set by the condition that equilibrium must be attained in reasonable times. EXPERIMENTAL MATERIALS AND TECHNIQUE The starting materials were mint gold (99.99 pct Au) and Mond nickel (99.9 pct Ni). Alloys, nominally 5 at. pct Ni and then each 10 at. pct across the system, were produced by vacuum-levitation melting compacts of mixed drillings of the pure metals. The nickel used for the reference tablets in the cells was melted in a similar manner. The alloy ingots, cast in boron nitride molds, were cold-forged and

Jan 1, 1967

By C. Dirksen

This study investigates whether oxygen consumption during segregated forward combustion may be affected by natural convection. Linear theory indicates that thermal instability occurs in a horizontal porous medium when the modified Rayleigh number N 'Ra exceeds a critical value of about 40. Most experimental results, including those described here, indicate this value to be about an order of magnitude smaller. N ', is derived from "differential similarity" and the proper time scale factor is also obtained. The critical value of N'ra for a horizontal, water-saturated porous medium at atmospheric pressure subjected to a uertical temperature gradient was found to be about 3.0. The ambiguity in the value of N'R, arising when fluid properties cannot be assumed constant is indicated. Natural convection was observed for oblique systems below N 'Ra , while simultaneous horizontal flow did not affect N Racrit. The expected range of values for the various parameters pertaining to segregated forward combustion is indicated and the corresponding values of N 'Ra calculated. Only under very favorable conditions, such as high permeability, high pressure and low top temperature, can the critical value of N 'R, be exceeded. Thickness of the convection layer should not become too large, since the time required to obtain significant mixing is proportional to the square of the thickness. For an oblique combustion frant the conditions for significant mixing may be less strenuous. LNTRODUCTION Laboratory1,2 and field314 experiments have shown that a markedly upgraded oil can be produced by in situ forward combustion. Under certain conditions injected air may move through a high permeability, gas-saturated channel over the oil-saturated layer, while combustion takes place, exclusively, at the horizontal interface (Fig. 1). Such a channel may be a natural gas cap, or it may result from a forward combustion process in which injected air and combustion gases fingered through the top of the formation, causing a premature breakthrough at the production well. In this particular case of segregated forward combustion, the air stream moves parallel to the combustion front. Molecular diffusion and transverse mechanical dispersion will be insufficient to cause all the oxygen in the air stream to reach the combustion front. When the oxygen in the air stream is not completely consumed in the combustion process, it will reach the production well and create a serious fire hazard. In addition, the reduced efficiency may make the process economically unprofitable while also serious corrosion problems may be experienced in the production we11.3 This undesirable situation should, therefore, be prevented. However, in a situation as depicted in Fig. 1, an unstable temperature gradient exists in the gas phase. The combustion is taking place at the lower boundary at a nearly constant temperature that may be anywhere from 600 to 1,200F, depending on the conditions. The upper boundary of the gas phase is overlying, impermeable rock; its temperature might be around 100F, but may increase to 300F or higher due to conduction and convection as the combustion process continues. This represents a steep temperature gradient and it is conceivable that under those conditions free or natural convection will take place in the gas

Jan 1, 1967

By E. S. Leaver

THE presence of soluble base metals in precious-metal ores usually precludes cyanidation as the best method of treatment. The laboratory experiments described in this paper show the possibility of cyanidation of gold-silver ores containing less than 0.5 per cent. of cyanide-soluble copper and the effect of zinc in the cyanide solution. PART 1.-COPPER IN CYANIDATION The proposed process of cyanidation of precious-metal ores containing copper is based on the regeneration of about 80 per cent. of the cyanide used in the dissolution of the copper. The method of regeneration involves a combination of the sulfide and the acid precipitation of the copper and silver. The resultant solution is made alkaline with lime, and the gold is precipitated with zinc dust.

Jan 1, 1929

By E. Gregory, C. G. Goetzel

The outstanding elevated temperature properties of materials made from sintered aluminum powder have been well established in recent years.1,2 and considerable investigation has been carried out on the structures which appear to be responsible for this type of strengthening.2,3 The maximum operating temperature of such materials is severely limited, however, by the low melting point of the aluminum matrix; and, therefore, considerable interest was aroused in methods of introducing the

Jan 1, 1959

By C. S. Smith, L. W. Kempf, C. S. Taylor

The thermal conductivity of aluminum alloys is of considerable industrial importance. This is particularly true in such applications as internal-combustion engines where one of the principal reasons for the use of these alloys is their relatively higher thermal conductivity. In spite of this, relatively few data are available on this property of aluminum alloys. The reason is quite apparent to anyone concerned with the experimental determination of coefficients of thermal conductivity. This determination, in theory so simple, is extraordinarily difficult if any high degree of precision is desired. Fortunately, some .knowledge of the relationship between thermal and electrical conductivity has permitted the use of the latter physical property in deducing the relative approximate values of the thermal conductivities of metals. This fundamental relationship, first enunciated by Wiedemann and Franz' as applying to metallic elements and later shown by Lorenz2 to be applicable to alloys within a single metallic system, has been of service in the industrial application of metals. The electrical conductivity of metals is easily determined with a high degree of precision. It is, therefore, quite desirable that the relationship between electrical and thermal characteristics be determined with the greatest possible precision. This paper presents data on the electrical and thermal conductivities of a number of aluminum alloys of industrial importance. Literature on Thermal Conductivity of Aluminum Alloys Masumoto3 determined the electrical and thermal conductivities of 18 aluminum alloys. His results indicated a relatively constant relationship between thermal and electrical conductivity.

Jan 1, 1937

By Benjamin N. Webber

The peninsula of Nicoya contains virtually all of the known manganese deposits of Costa Rica. These are south and west of the Tempisque River, which flows across the peninsula near its juncture with the mainland. This peninsula forms the westernmost part of the province of Guana-caste, which is the northern. of the two Pacific Coast provinces of Costa Rica. The larger villages are connected by ox-cart roads and trails. The area may be covered on horseback without difficulty except during the rainy season, when rivers are in flood and difficult to ford. This is particularly true of the Rio Seco-Guay-jiniquil area, where there are no inhabitants and few open trails through the tropical jungle. Santa Cruz and Sardinal are served by the Taca Airlines, two planes a week from San Jose and Puntarenas. The port of Puntarenas has excellent loading facilities but none are available nearer the manganese districts; there ore must be lightered to vessels standing offshore. Physiography In Costa Rica there are three physiographic divisions: (I) the central plateau (Mesa Central), a somewhat dissected lava platform upon which are superimposed volcanic peaks, some of which are still active; (2) the Atlantic lowlands and (3) the Pacific lowlands. The peninsula of Nicoya and the larger part of the province of Guanacaste lie within the Pacific low- lands. The term "lowland" indicates relation to the central plateau, as the peninsula of Nicoya is largely mountainous. The mountains of Nicoya form the southern extremity of a range of low hills, which are almost continuous along the Costa Rican coast to the Nicaraguan border. The coast line shows evidence of subsidence. The Gulf of Nicoya obviously is the drowned valley of the Tempisque River. The west coast of Nicoya shows many rocks, shoals, bays, inlets and small islands as evidence of a sea encroachment. The altitude of the manganese deposits ranges from 0 to 800 ft. Topography is of the mature type of wide valleys and low hills, often with abrupt slopes. The climate is tropical and humid; rainfall of 125 in. falls largely between Sept. I and Jan. I. Vegetation often is very dense, the Rio Seco-Guayjiniquil area being truly tropical jungle, containing many hardwoods. History and Production The production of manganese ore in Costa Rica apparently dates from the first World War. It reached a peak of about 10,000 tons in the year 1919, then declined rapidly. Evidence of this period of prospecting has rotted away or been swallowed by the jungle. The war now in progress apparently revived the interest in Costa Rican manganese and has encouraged further prospecting. Deposits long known have been redenounced and trails have been cut through the jungle to them. Many new deposits have been discovered in the last

Jan 1, 1949

By Benjamin N. Webber

The peninsula of Nicoya contains virtually all of the known manganese deposits of Costa Rica. These are south and west of the Tempisque River, which flows across the peninsula near its juncture with the mainland. This peninsula forms the westernmost part of the province of Guana-caste, which is the northern. of the two Pacific Coast provinces of Costa Rica. The larger villages are connected by ox-cart roads and trails. The area may be covered on horseback without difficulty except during the rainy season, when rivers are in flood and difficult to ford. This is particularly true of the Rio Seco-Guay-jiniquil area, where there are no inhabitants and few open trails through the tropical jungle. Santa Cruz and Sardinal are served by the Taca Airlines, two planes a week from San Jose and Puntarenas. The port of Puntarenas has excellent loading facilities but none are available nearer the manganese districts; there ore must be lightered to vessels standing offshore. Physiography In Costa Rica there are three physiographic divisions: (I) the central plateau (Mesa Central), a somewhat dissected lava platform upon which are superimposed volcanic peaks, some of which are still active; (2) the Atlantic lowlands and (3) the Pacific lowlands. The peninsula of Nicoya and the larger part of the province of Guanacaste lie within the Pacific low- lands. The term "lowland" indicates relation to the central plateau, as the peninsula of Nicoya is largely mountainous. The mountains of Nicoya form the southern extremity of a range of low hills, which are almost continuous along the Costa Rican coast to the Nicaraguan border. The coast line shows evidence of subsidence. The Gulf of Nicoya obviously is the drowned valley of the Tempisque River. The west coast of Nicoya shows many rocks, shoals, bays, inlets and small islands as evidence of a sea encroachment. The altitude of the manganese deposits ranges from 0 to 800 ft. Topography is of the mature type of wide valleys and low hills, often with abrupt slopes. The climate is tropical and humid; rainfall of 125 in. falls largely between Sept. I and Jan. I. Vegetation often is very dense, the Rio Seco-Guayjiniquil area being truly tropical jungle, containing many hardwoods. History and Production The production of manganese ore in Costa Rica apparently dates from the first World War. It reached a peak of about 10,000 tons in the year 1919, then declined rapidly. Evidence of this period of prospecting has rotted away or been swallowed by the jungle. The war now in progress apparently revived the interest in Costa Rican manganese and has encouraged further prospecting. Deposits long known have been redenounced and trails have been cut through the jungle to them. Many new deposits have been discovered in the last

Jan 1, 1949

By S. N. Kesten, Richard Murphy, A. H. Land, W. F. James

Introduction—by W. F. James and A. H. Lang This paper describes the geology and present state of development of uranium and thorium deposits in Canada. It is expected that this information will be added to that now being assembled from available American and British data to provide a background for engineers and others who may be called upon in the future to examine or search for radioactive deposits. Some generaliza- tions regarding the Canadian deposits are included, but many of these are necessarily tentative. The information contained in the paper is up to date for the end of 1948. The information contained in this paper has been derived from many sources. Much of it is from the records of the Canadian government-owned Eldorado Mining and Refining (1944) Limited and from examinations of government and private properties made by officers of the Geological Survey of Canada. Some information on privately-owned properties has been quoted from other sources mentioned in the text. The information has been assembled by W. F. James of Eldorado Mining and Refining (1944) Limited and A. H. Lang of the Geological Survey of Canada, who have written the sections for which they are credited. The description of the Eldorado mine is based on reports by Richard Murphy, formerly chief geologist for Eldorado; the report by Mr. Murphy was published previously by the Canadian Institute of Mining and Metallurgy,' to whom the writers are indebted for permission to repub-lish. The section dealing with the geology of and development work in the Goldfields area, where Eldorado has important holdings, is by S. N. Kesten, field geologist for Eldorado. The geological diagram of the Goldfields area (fig. 2) was kindly supplied by A. M. Christie of the Geological Survey of Can-

Jan 1, 1951

By W. F. James, Richard Murphy, S. N. Kesten, A. H. Land

Introduction—by W. F. James and A. H. Lang This paper describes the geology and present state of development of uranium and thorium deposits in Canada. It is expected that this information will be added to that now being assembled from available American and British data to provide a background for engineers and others who may be called upon in the future to examine or search for radioactive deposits. Some generaliza- tions regarding the Canadian deposits are included, but many of these are necessarily tentative. The information contained in the paper is up to date for the end of 1948. The information contained in this paper has been derived from many sources. Much of it is from the records of the Canadian government-owned Eldorado Mining and Refining (1944) Limited and from examinations of government and private properties made by officers of the Geological Survey of Canada. Some information on privately-owned properties has been quoted from other sources mentioned in the text. The information has been assembled by W. F. James of Eldorado Mining and Refining (1944) Limited and A. H. Lang of the Geological Survey of Canada, who have written the sections for which they are credited. The description of the Eldorado mine is based on reports by Richard Murphy, formerly chief geologist for Eldorado; the report by Mr. Murphy was published previously by the Canadian Institute of Mining and Metallurgy,' to whom the writers are indebted for permission to repub-lish. The section dealing with the geology of and development work in the Goldfields area, where Eldorado has important holdings, is by S. N. Kesten, field geologist for Eldorado. The geological diagram of the Goldfields area (fig. 2) was kindly supplied by A. M. Christie of the Geological Survey of Can-

Jan 1, 1951

By M. E. Straumanis, J. -P. Krumme

In basic ([KOH + KCl] with a total polarity of 2) or acidic (2N H2SO4) electrolytes and at anodic current densities of more thun 2 to 4 ma per sq cnz, n-type GaAs single crystals of lozo resistivity preferentially dissol~je forming etch tunnels with triangular or civc~ilay cross sections and of a width between 0.5 arid 5 p. These etch tunnels are oriented along any one of the four possible (111) directions of GaAs. However, their growth occurs only in one direction of a given (111) whick apparently is determined by the atomic sequence Ga —As (and not the rezlerse) in respect to an individual valence bridge in the crystal. It is concluded from comparison with the cubic lattice structure of GaAs that the etch tunnels represent macroscopic evidence for the tetrahedral bonds and their polar properties. If the anodic current density is increased the tunnel fomation results in the development of a fibrous surface layer consisting of GaAs. The latter separates frorn the substrate (in an anodic s~irface disintegration process) by the growth pressure of an As,0, filnz forming in the interior of the fibrous layer, 100 to 200 µ under the surface, at more than about 50 ma per sq cni. The fibrous GaAs film has the same crystallographic orientation as the substvate and represents a skeleton of the original crystal. Since the etch-tunnel density in a separated GaAs layer is about 108 c?n-', and the etch tunnels develop only along (111) in a given polar direction, it is assurraed tlmt the dislocations have no influence on the growth of these tunnels. ElECTROLYTIC treatment of smooth surfaces of poly- and single-crystalline GaAs at high anodic current densities causes the formation of porous surface layers.' This phenomenon suggests comparison with effects being observed with magnesium,' indium,, gallium,4 and aluminum5 and known as "anodic disintegration". The purpose of the present paper is to explore and to explain the reasons for the formation of such surface layers on GaAs and, in particular, to investigate the influence of the lattice polarity of this III-V compound semiconductor in the (111) direction on the anodic dissolution behavior. GaAs SINGLE CRYSTALS For the experiments described below GaAs single crystals from the Monsanto Co., St. Louis, Mo., were used. Their impurity levels were below 1 ppm and their dopant levels between 1 and 100 ppm. They were grown in (111) using the Czochralski or the gradient-freeze technique. The crystals had n-type conductivity and electric resistivities between 1 and 5 ohm-cm. EXPERIMENTAL The GaAs single-crystal rods were cut perpendicularly to (111) into wafers of about 1 mm thickness using a wire-blade crystal slicer and an aqueous slurry of Sic or a diamond saw. The orientation of the faces of these wafers were checked by Laue back-reflection patterns. If there was a deviation from (111) the faces were abraded under a certain angle using grinding paper and distilled water. The damaged surface layer was removed from each crystal by chemical etching with a mixture of 1HF:1HNO3: 1H20 or 2HF:1HNO3:2HAc (glacial). {110) faces were obtained by mechanical cleavage, producing surfaces which did not require a further treatment. The GaAs wafers were mounted using "alligator" clamps instead of soldered electrical contacts.' Only the bare crystal surfaces were dipped into the electrolyte. The clamps were coated with insulating wax to prevent any contact with the electrolyte. The experiments were carried out in aqueous 2 N H2so4,' or in an aqueous solution of KOH and KCl1 (1 mole KOH + 1 mole KCl in 1000 cu cm solution). Anodic current densities up to several hundred ma per sq cm were applied for periods between 30 sec and 2 hr. For the purpose of investigating the initial steps of disintegration the anodic current density applied never exceeded 20 ma per sq cm. The films which partially separated from the anodic surfaces under high-field conditions were treated with KOH to further their detachment by dissolving the As2O3 formed. The washed and dried films were pasted to strips of filter paper, and Laue pictures were made. The back-reflection patterns obtained were compared with those of the original anode surface before and after anodic dissolution. Furthermore, space reciprocal lattices7 were constructed from asymmetric rotation crystal patternsa which permitted the determination of the crystallographic orientation of the detached films of the corrugated anodic surfaces. The disintegration products were identified from assymmetric powder patterns.8 The polarity of the {111) faces was determined by chemical etching with mixtures of 1HF:1H2O2(30 pct): 2H2O or 1HNO3:2H2O. Different patterns on each of two inverse (111) sides appeared.'-l8 The correlation of these patterns to the Ga{111) or the As(111) side has already been established by the use of light figures,18-20 by X-ray diffraction near the absorption edges of gallium and arsenic,'lmZ4 and by LEED measurements.25 The geometric structure of these surfaces and the interior of the anodically attacked crystals were observed and photographed with a high-power microscope using oil immersion objectives up to magnification of X1720.

Jan 1, 1968